Effect of metal ions in organic synthesis. Part XXXI. Synthesis of new 3-carbonyl- and 3-carboxy-1-heterocyclaminopyrroles by copper(II) chloride-catalyzed reaction of heterocyclic azoalkenes

The direct synthesis of a new class of unknown 1-heterocyclamino-3-carbonylpyrroles and 1-heterocyclamino-3-carboxypyrroles by copper(II) chloride-catalyzed reaction of heterocyclic conjugated azoalkene derivatives with β-diketones and β-ketoesters is reported.     

1,3-Cycloaddition of nitrones in ionic liquids catalyzed by Er(III): an easy access to isoxazolidines

1,3-Dipolar cycloadditions of nitrones with alkenes afforded the corresponding isoxazolidines in ionic liquids in the presence of Er(OTf)₃. The ionic liquid and the catalyst are recycled up to five times without any specific treatment or loss of activity. Extension of the procedure to the synthesis of isoxazolidinyl nucleosides has been investigated.     

Exact controllability of a spherical cap: Numerical implementation of HUM

This paper deals with the numerical implementation of the exact boundary controllability of the Reissner model for shallow spherical shells (Ref. 1). The problem is attacked by the Hilbert uniqueness method (HUM, Refs. 2–4), and we propose a semidiscrete method for the numerical approximation of the minimization problem associated to the exact controllability problem. The numerical results compare well with the results obtained by a finite difference and conjugate gradient method in Ref. 5.This work was done when the first two authors were at CNR-IAC, Rome, Italy as Graduate Students.     

A parallel domain reduction method

We relate a particular version of a parallel multigrid method to a domain decomposition method, showing that the parallel multigrid method reduces computation to a small portion of the domain and then extends the solution to the entire domain using the correct reflections to get the exact solution. We extend a particular example to double the parallelism in a nonobvious manner. While the techniques of this paper are applied to twodimensional problems, they can be applied to higher dimensional problems in an obvious manner.     

Enhanced nonlinear effects in pulse propagation through epsilon‐near‐zero media

In recent years, unconventional metamaterial properties have triggered a revolution of electromagnetic research which has unveiled novel scenarios of wave‐matter interaction. A very small dielectric permittivity is a leading example of such unusual features, since it produces an exotic static‐like regime where the electromagnetic field is spatially slowly‐varying over a physically large region. The so‐called epsilon‐near‐zero metamaterials thus offer an ideal platform where to manipulate the inner details of the “stretched” field. Here we theoretically prove that a standard nonlinearity is able to operate such a manipulation to the point that even a thin slab produces a dramatic nonlinear pulse transformation, if the dielectric permittivity is very small within the field bandwidth. The predicted non‐resonant releasing of full nonlinear coupling produced by the epsilon‐near‐zero condition does not resort to any field enhancement mechanism and opens novel routes to exploiting matter nonlinearity for steering the radiation by means of ultra‐compact structures.

     

Multicomponent diffusion in nanosystems

We present the detailed analysis of the diffusive transport of spatially inhomogeneous fluid mixtures and the interplay between structural and dynamical properties varying on the atomic scale. The present treatment is based on different areas of liquid state theory, namely, kinetic and density functional theory and their implementation as an effective numerical method via the lattice Boltzmann approach. By combining the first two methods, it is possible to obtain a closed set of kinetic equations for the singlet phase space distribution functions of each species. The interactions among particles are considered within a self-consistent approximation and the resulting effective molecular fields are analyzed. We focus on multispecies diffusion in systems with short-range hard-core repulsion between particles of unequal sizes and weak attractive long-range interactions. As a result, the attractive part of the potential does not contribute explicitly to viscosity but to diffusivity and the thermodynamic properties. Finally, we obtain a practical scheme to solve the kinetic equations by employing a discretization procedure derived from the lattice Boltzmann approach. Within this framework, we present numerical data concerning the mutual diffusion properties both in the case of a quiescent bulk fluid and shear flow inducing Taylor dispersion.     

Time series hyperspectral chemical imaging data: challenges, solutions and applications

Hyperspectral chemical imaging (HCI) integrates imaging and spectroscopy resulting in three-dimensional data structures, hypercubes, with two spatial and one wavelength dimension. Each spatial image pixel in a hypercube contains a spectrum with >100 datapoints. While HCI facilitates enhanced monitoring of multi-component systems; time series HCI offers the possibility of a more comprehensive understanding of the dynamics of such systems and processes. This implies a need for modeling strategies that can cope with the large multivariate data structures generated in time series HCI experiments. The challenges posed by such data include dimensionality reduction, temporal morphological variation of samples and instrumental drift. This article presents potential solutions to these challenges, including multiway analysis, object tracking, multivariate curve resolution and non-linear regression. Several real world examples of time series HCI data are presented to illustrate the proposed solutions.     

Diastereoselective total synthesis of (+)-13-stemarene by fourth generation methods: a formal total synthesis of (+)-18-deoxystemarin

The problem of constructing diastereoselectively the C/D ring system of stemarane diterpenes from a bicyclo[2.2.2]octane intermediate was solved resulting in very simple synthesis of (+)-13-stemarene 1. The obtaining of the latter represents also a formal synthesis of (+)-18-deoxystemarin 2. In the key step, the epimeric mixture 10, dissolved in toluene, was converted by the action of TsOH into (+)-stemar-13-en-15-one 28.